Photoelectric conversion element and photoelectric conversion element module

ABSTRACT

There are provided a photoelectric conversion element and a photoelectric conversion element module including the photoelectric conversion element, the photoelectric conversion element including a transparent substrate, a first and second transparent conductive layer arranged on the transparent substrate, a photoelectric conversion layer arranged on the first transparent conductive layer, a porous insulating layer covering the photoelectric conversion layer, a reflective layer arranged on the porous insulating layer, and a counter conductive layer that are arranged on the reflective layer, in which the photoelectric conversion layer contains a porous semiconductor, a carrier-transport material, and a photosensitizer, and in which an area of the orthogonal projection of the porous insulating layer onto the transparent substrate and an area of the orthogonal projection of the reflective layer onto the transparent substrate are each larger than an area of the orthogonal projection of the photoelectric conversion layer onto the transparent substrate.

This application is a continuation-in-part of U.S. patent applicationSer. No. 14/124,788 (pending) filed Dec. 9, 2013, entitled“Photoelectric Conversion Element and Photoelectric Conversion ElementModule (pending), which is the National phase of PCT applicationPCT/JP2012/064527 filed Jun. 6, 2012, which claims priority of Japanesepatent application 2011-128075 filed Jun. 8, 2011, the entire contentsof each of which is incorporated herein by reference.

TECHNICAL FIELD

The present invention relates to a photoelectric conversion element anda photoelectric conversion element module.

BACKGROUND ART

Solar cells capable of converting sunlight into electric power have beenreceiving attention as energy sources to replace fossil fuels. Nowadays,solar cells including crystalline silicon substrates and thin-filmsilicon solar cells are practically used. However, the former solarcells have the problem of high production costs of silicon substrates.The latter thin-film solar cells have the problem of high productioncosts due to the need to use various types of gases for use in theproduction of semiconductors and complicated devices. Thus, in any typeof solar cell, continuing efforts have been made to reduce the cost perpower output by improving photoelectric conversion efficiency. However,the foregoing problems have not yet been solved.

For example, Japanese Patent No. 2664194 (PTL 1) reports, as a new typeof solar cell, a photoelectric conversion element on the basis ofphotoinduced electron transfer in a metal complex. The structure of thephotoelectric conversion element is as follows: A photoelectricconversion layer on which a photosensitizing dye adsorbs to have anabsorption spectrum in the visible light region and an electrolyticsolution are held between two glass substrates. A first electrode and asecond electrode are arranged on respective surfaces of the two glasssubstrates.

The irradiation with light from the first electrode side generateselectrons in the photoelectric conversion layer. The generated electronsare transferred from the first electrode to the opposite secondelectrode through an external electric circuit. The transferredelectrons are transported by ions in an electrolyte and return to thephotoelectric conversion layer. Electric energy can be taken from thesuccessive transfer of electrons.

The photoelectric conversion element described in PTL 1 has a structurein which a gap between the two glass substrates is filled with theelectrolytic solution. Thus, prototype solar cells with small areas canbe produced. However, it is difficult to produce a large-area solarcell, for example, a 1 m×1 m square solar cell. That is, in the case ofincreasing the area of a solar cell, a generation current increases withincreasing area. However, the in-plane resistance of the first electrodeis increased to increase internal series resistance as a solar cell.This disadvantageously leads to a decrease in fill factor (FF) incurrent-voltage characteristics during photoelectric conversion.

As attempts to overcome the foregoing problem, for example, JapaneseUnexamined Patent Publication (Translation of PCT Application) No.11-514787 (PTL 2), Japanese Unexamined Patent Application PublicationNo. 2001-357897 (PTL 3), and Japanese Unexamined Patent ApplicationPublication No. 2002-367686 (PTL 4) report photoelectric conversionelement modules each including a plurality of photoelectric conversionelements connected in series. In each of the photoelectric conversionelement modules, the increase in internal series resistance is inhibitedby electrically connecting an electrode (conductive layer) of thephotoelectric conversion element to an electrode (counter conductivelayer) of an adjacent photoelectric conversion element.

FIG. 3 is a schematic cross-sectional view of the structure of aconventional photoelectric conversion element. In a conventionalphotoelectric conversion element 40, a transparent conductive layer 42is arranged on a transparent substrate 41 as illustrated in FIG. 3. Alaminate is arranged on the transparent conductive layer 42, thelaminate including a porous semiconductor 43 on which a dye adsorbs, areflective layer 45, a porous insulating layer 44, a catalyst layer 46,and a counter conductive layer 47 stacked in that order. The transparentsubstrate 41 and the supporting substrate 48 are fixed with a sealingmember 49 in such a manner that a supporting substrate 48 is arrangedabove the counter conductive layer 47. The laminate is sealed with thetransparent substrate 41, the supporting substrate 48, and the sealingmember 49. A space in the photoelectric conversion element 40 is filledwith a carrier-transport material 51.

In the conventional photoelectric conversion element illustrated in FIG.3, a material constituting the reflective layer 45 is different fromthat of the porous insulating layer 44. Thus, delamination is liable tooccur between the reflective layer 45 and the porous insulating layer44. Furthermore, the reflective layer 45 is formed of fine grains havinga relatively large size of 100 nm or more and thus has insufficientlayer strength. Thus, the delamination is liable to occur between thereflective layer 45 and the porous insulating layer 44.

In Japanese Unexamined Patent Application Publication No. 2010-262760(PTL 5), the stacking sequence of the porous semiconductor, thereflective layer, and the porous insulating layer is changed in order toprevent the delamination between the reflective layer and the porousinsulating layer. The change in stacking sequence inhibits delaminationthat is liable to occur between layers, thereby producing thephotoelectric conversion element in high yield.

CITATION LIST Patent Literature

PTL 1: Japanese Patent No. 2664194

PTL 2: Japanese Unexamined Patent Publication (Translation of PCTApplication) No. 11-514787

PTL 3: Japanese Unexamined Patent Application Publication No.2001-357897

PTL 4: Japanese Unexamined Patent Application Publication No.2002-367686

PTL 5: Japanese Unexamined Patent Application Publication No.2010-262760

SUMMARY OF INVENTION Technical Problem

In the photoelectric conversion element described in PTL 5, it ispossible to prevent the delamination between layers. However, thereflective layer is not arranged in the direction of a side surface ofthe photoelectric conversion layer because of the fact that the porousinsulating layer is arranged between the photoelectric conversion layerand the reflective layer and that the reflective layer is arranged justin the same shape as the photoelectric conversion layer. Thus, thelight-scattering effect of the reflective layer is not sufficientlyprovided, thereby disadvantageously reducing the photoelectricconversion efficiency of the photoelectric conversion element.

The present invention has been accomplished in light of the foregoingcircumstances. It is an object of the present invention to provide aphotoelectric conversion element having high photoelectric conversionefficiency and a photoelectric conversion element module by suppressingthe fact that a porous insulating layer inhibits the light-scatteringeffect of a reflective layer and by improving the scattering effect oflight from the direction of the side surface.

Solution to Problem

To overcome the foregoing problems, the inventors have conductedintensive studies and have found that, in a photoelectric conversionelement and a photoelectric conversion element module, it is possible toimprove the light-scattering effect of a reflective layer by forming thereflective layer having a larger projected area onto a transparentsubstrate than a porous semiconductor. This finding has led to thecompletion of the present invention.

A photoelectric conversion element of the present invention includes atransparent substrate, a transparent conductive layer arranged on thetransparent substrate, a photoelectric conversion layer arranged on thetransparent conductive layer, a porous insulating layer arranged incontact with the photoelectric conversion layer, a reflective layerarranged in contact with the porous insulating layer, and a catalystlayer and a counter conductive layer that are arranged on the reflectivelayer, in which the photoelectric conversion layer contains a poroussemiconductor, a carrier-transport material, and a photosensitizer, andin which the area of the orthogonal projection of the porous insulatinglayer onto the transparent substrate and the area of the orthogonalprojection of the reflective layer onto the transparent substrate areeach larger than the area of the orthogonal projection of thephotoelectric conversion layer onto the transparent substrate.

The porous insulating layer is preferably arranged in contact with anupper portion of the photoelectric conversion layer. The reflectivelayer is preferably arranged in contact with an upper portion of theporous insulating layer. The porous insulating layer preferably has athickness of 0.2 μm or more and 5 μm or less. The total thickness of theporous insulating layer and the reflective layer is preferably 10 μm ormore.

The porous insulating layer is preferably composed of a material havingan electrical conductivity of 1×10¹² Ω·cm or less. The porous insulatinglayer is preferably composed of one or more compounds selected from thegroup consisting of niobium oxide, zirconium oxide, silicon oxidecompounds, aluminum oxide, and barium titanate.

The reflective layer preferably contains aluminum oxide or titaniumoxide. The reflective layer is preferably composed of a materialidentical to a material constituting the porous semiconductor. Thereflective layer and the porous semiconductor are preferably composed oftitanium oxide. The reflective layer is preferably formed of fineparticles having an average particle size larger than the averageparticle size of fine particles constituting the porous semiconductor.

The present invention provides a photoelectric conversion element moduleincluding two or more photoelectric conversion elements electricallyconnected in series, in which at least one of the photoelectricconversion elements is the photoelectric conversion element of thepresent invention.

The present invention provides a photoelectric conversion element moduleincluding three or more photoelectric conversion elements electricallyconnected in series and/or parallel, in which at least one of thephotoelectric conversion elements is the photoelectric conversionelement of the present invention.

The present invention provides a photoelectric conversion element moduleincluding two or more photoelectric conversion elements electricallyconnected in series and/or parallel, in which each of the photoelectricconversion elements is the photoelectric conversion element of thepresent invention.

Advantageous Effects of Invention

According to the present invention, a photoelectric conversion elementhaving high photoelectric conversion efficiency and a photoelectricconversion element module are provided by improving the light-scatteringeffect of a reflective layer.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic cross-sectional view of an example of thestructure of a photoelectric conversion element of the presentinvention.

FIG. 2 is a schematic cross-sectional view of an example of thestructure of a photoelectric conversion element module of the presentinvention.

FIG. 3 is a schematic cross-sectional view of an example of thestructure of a conventional photoelectric conversion element.

DESCRIPTION OF EMBODIMENTS

A photoelectric conversion element and a photoelectric conversionelement module of the present invention will be described below withrespect to the drawings. In the drawings of the present invention, thesame or equivalent portions are designated using the same referencenumerals. The dimensions, such as length, width, and depth, areappropriately changed for clarification and simplification of thedrawings and do not represent actual dimensions.

<Photoelectric Conversion Element>

FIG. 1 is a schematic cross-sectional view of an example of thestructure of a photoelectric conversion element of the presentinvention. As illustrated in FIG. 1, a photoelectric conversion element10 of the present invention includes a transparent substrate 1, atransparent conductive layer 2 on the transparent substrate 1, aphotoelectric conversion layer 3 on the transparent conductive layer 2,a porous insulating layer 4 in contact with the photoelectric conversionlayer 3, a reflective layer 5 in contact with the porous insulatinglayer 4, and a catalyst layer 6 on the reflective layer 5. Thephotoelectric conversion layer 3 contains a porous semiconductor, acarrier-transport material, and a photosensitizer. The area of theorthogonal projection of the porous insulating layer 4 onto thetransparent substrate 1 and the area of the orthogonal projection of thereflective layer 5 onto the transparent substrate 1 are each larger thanthe area of the orthogonal projection of the photoelectric conversionlayer 3 onto the transparent substrate 1. This structure improves thelight-scattering effect of the reflective layer 5 to increase thephotoelectric conversion efficiency of the photoelectric conversionelement.

The carrier-transport material is filled into gaps among the porousinsulating layer 4, the reflective layer 5, and the catalyst layer 6 inaddition to the photoelectric conversion layer 3. A counter conductivelayer 7 is arranged on the catalyst layer 6. The transparent substrate 1and a supporting substrate 8 are fixed with a sealing member 9. Thetransparent conductive layer 2 is partially broken. The broken portionis referred to as a scribe line 2′. Hereinafter, components included inthe photoelectric conversion element 10 of the present invention will bedescribed.

<<Transparent Substrate>>

In the present invention, at least a light-receiving surface of thetransparent substrate 1 needs to have optical transparency, so thetransparent substrate 1 needs to be composed of an optically transparentmaterial. However, the transparent substrate 1 need not necessarilytransmit all light having any wavelength and may be composed of amaterial substantially transparent to light having a wavelengtheffectively sensitive to a dye, as described below. The transparentsubstrate 1 preferably has a thickness of about 0.2 to about 5 mm.

A material for the transparent substrate 1 is not particularly limitedas long as it is commonly used for solar cells. For example, glasssubstrates composed of soda-lime glass, fused silica glass, crystallinesilica glass, and so forth and heat-resistant resin sheets, such asflexible films, may be used. With respect to flexible films,tetraacetylcellulose (TAC), polyethylene terephthalate (PET),polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate (PA),polyetherimide (PEI), phenoxy resins, and Teflon (registered trademark)are exemplified.

In the case where another member is formed on the transparent substrate1 under heating, in other words, for example, in the case where thephotoelectric conversion layer 3 composed of a porous semiconductor isformed on the transparent substrate under heating at about 250° C.,Teflon (registered trademark) is preferably used as the transparentsubstrate 1 because Teflon (registered trademark) has a heat resistanceof 250° C. or higher. The transparent substrate 1 may be used as a basethat serves to be attached to another structure. That is, thetransparent substrate 1 may be easily attached to another structure atits periphery with a machined metal part and a screw.

<<Transparent Conductive Layer>>

In the present invention, the transparent conductive layer 2 may becomposed of a material that substantially transmits light having awavelength effectively sensitive to a photosensitizer described below.The transparent conductive layer 2 need not necessarily transmit alllight having any wavelength. Examples of the material include complexindium tin oxide (ITO), tin oxide (SnO₂), fluorine-doped tin oxide(FTO), zinc oxide (ZnO), and titanium oxide doped with tantalum orniobium.

The transparent conductive layer 2 may be formed on the transparentsubstrate 1 by a known method, for example, a sputtering method or aspray method. The transparent conductive layer 2 has a thickness ofabout 0.02 to about 5 μm. The transparent conductive layer 2 preferablyhas a lower resistance and more preferably has a resistance of 40 Ω/sqor less.

In the case where the transparent substrate 1 composed of soda-limefloat glass is used, the transparent conductive layer 2 composed of FTOis preferably stacked on the transparent substrate 1. A commerciallyavailable transparent substrate 1 provided with a transparent conductivelayer 2 may be used.

<<Photoelectric Conversion Layer>>

In the present invention, the photoelectric conversion layer 3 containsthe porous semiconductor, the carrier-transport material, and thephotosensitizer, the photosensitizer being adsorbed on the poroussemiconductor. In the photoelectric conversion layer 3 having such astructure, the carrier-transport material can move inside and outsidethe layer.

(Porous Semiconductor)

The type of the porous semiconductor contained in the photoelectricconversion layer 3 is not particularly limited as long as it is commonlyused for a photoelectric conversion material. Examples of the poroussemiconductor that may be used include semiconductors, such as titaniumoxide, zinc oxide, tin oxide, iron oxide, niobium oxide, cerium oxide,tungsten oxide, barium titanate, strontium titanate, cadmium sulfide,lead sulfide, zinc sulfide, indium phosphide, copper-indium sulfide(CuInS₂), CuAlO₂, and SrCu₂O₂, and combinations thereof. Among thesecompounds, titanium oxide is particularly preferred in view of stabilityand safety.

Examples of titanium oxide suitably used for the porous semiconductorinclude anatase titanium oxide, rutile titanium oxide, amorphoustitanium oxide, various titanium oxides, such as metatitanic acid andorthotitanic acid, in a narrow sense, titanium hydroxide, and hydroustitanium oxide. These compounds may be used separately or in combinationof two or more as a mixture. With respect to the two types ofcrystalline titanium oxide, anatase and rutile, the structure depends onthe production process and the heat history. As the titanium oxidecontained in the porous semiconductor, a higher anatase titanium oxidecontent is preferred. An anatase titanium oxide content of 80% or moreis more preferred.

The porous semiconductor may be monocrystalline or polycrystalline. Theporous semiconductor is preferably polycrystalline in view of stability,ease of crystal growth, production cost, and so forth. The poroussemiconductor is preferably formed of nano- to micro-scale semiconductorfine particles. Titanium oxide fine particles are more preferably used.Titanium oxide fine particles may be produced by a known method, forexample, a gas-phase method, a liquid-phase method (hydrothermalsynthesis and a sulfuric acid method). Furthermore, titanium oxide fineparticles may be produced by high-temperature hydrolysis of a chloride,developed by Degussa.

As the semiconductor fine particles contained in the poroussemiconductor, a semiconductor compound having a uniform composition maybe used. Alternatively, a mixture of two or more semiconductor compoundshaving different compositions may be used. With respect to the particlesize of the semiconductor fine particles, the semiconductor fineparticles having an average particle size of about 100 to about 500 nmmay be used. The semiconductor fine particles having an average particlesize of about 5 nm to about 50 nm may also be used. Alternatively, amixture of these semiconductor fine particles may be used. Thesemiconductor fine particles having a particle size of about 100 toabout 500 nm seemingly contribute to the scattering of incident light toimprove light-harvesting efficiency. The semiconductor fine particleshaving an average particle size of about 5 nm to about 50 nm seeminglycontribute to an increase in the number of adsorption sites to improvethe amount of dye adsorbed.

In the case where the porous semiconductor is formed of a mixture of twoor more types of semiconductor fine particles having different particlesizes, the average particle size of the semiconductor fine particleshaving a smaller particle size is preferably 10 or more times that ofthe semiconductor fine particles having a larger particle size. In thecase where the mixture of two or more types of semiconductor fineparticles is used, it is effective to use a semiconductor compoundhaving a strong adsorption effect in the form of semiconductor fineparticles having a small particle size.

The thickness of the porous semiconductor, i.e., the thickness of thephotoelectric conversion layer 3, is not particularly limited. Forexample, the photoelectric conversion layer 3 preferably has a thicknessof about 0.1 to about 100 μm. The porous semiconductor preferably has alarge surface area of, for example, about 10 to 200 m²/g.

(Photosensitizer)

The photosensitizer that is adsorbed on the porous semiconductor isarranged to convert the energy of light incident on the photoelectricconversion element into electric energy. To allow the photosensitizer toadsorb firmly on the porous semiconductor, the photosensitizerpreferably contains an interlocking group in its molecule. In general,the interlocking group refers to a group that intervenes when a dye isfixed to the porous semiconductor and provides an electrical coupling tofacilitate electron transfer between the dye in an excited state and aconduction band of the semiconductor. Specific examples thereof includefunctional groups, such as a carboxyl group, an alkoxy group, a hydroxylgroup, a sulfonic group, an ester group, a mercapto group, and aphosphonyl group.

As the photosensitizer adsorbed on the porous semiconductor, forexample, various organic dyes and metal complex dyes that haveabsorption in the visible light region and the infrared region may beused. These dyes may be used separately or in combination of two ormore. In general, extinction coefficients of organic dyes are largerthan those of metal complex dyes described below.

Examples of the organic dyes include azo dyes, quinone dyes, quinoniminedyes, quinacridone dyes, squarylium dyes, cyanine dyes, merocyaninedyes, triphenylmethane dyes, xanthene dyes, porphyrin dyes, perylenedyes, indigo dyes, and naphthalocyanine dyes.

The metal complex dyes are compounds each having a structure in which atransition metal is coordinated to a metal atom. Examples of such metalcomplex dyes include porphyrin-based dyes, phthalocyanine-based dyes,naphthalocyanine-based dyes, and ruthenium-based dyes. Examples of themetal atom contained in the metal complex dyes include Cu, Ni, Fe, Co,V, Sn, Si, Ti, Ge, Cr, Zn, Ru, Mg, Al, Pb, Mn, In, Mo, Y, Zr, Nb, Sb,La, W, Pt, Ta, Ir, Pd, Os, Ga, Tb, Eu, Rb, Bi, Se, As, Sc, Ag, Cd, Hf,Re, Au, Ac, Tc, Te, and Rh. Specifically, phthalocyanine-based dyes anddyes in which metals are coordinated to ruthenium-based dyes arepreferred. Ruthenium-based metal complex dyes are particularlypreferred.

In particular, ruthenium-based metal complex dyes represented byformulae (1) to (3) are preferred. Examples of commercially availableruthenium-based metal complex dyes include Ruthenium 535 dye, Ruthenium535-bisTBA dye, and Ruthenium 620-1H3TBA dye, which are trade names andmanufactured by Solaronix.

<<Carrier-Transport Material>>

In the present invention, all spaces and gaps in the photoelectricconversion element 10 illustrated in FIG. 1 are filled with thecarrier-transport material. In other words, a carrier-transport material11 is contained in a region surrounded by the transparent conductivelayer 2, the supporting substrate 8, and the sealing member 9 asillustrated in FIG. 1. Furthermore, gaps among the photoelectricconversion layer 3, the porous insulating layer 4, the reflective layer5, and the catalyst layer 6 are also filled with the carrier-transportmaterial. In this specification, for convenience sake, thecarrier-transport material 11 indicates a region that does not includeanother component and that is filled with only the carrier-transportmaterial.

The carrier-transport material is composed of a conductive materialcapable of transporting ions. Examples of the conductive material thatmay be suitably used include liquid electrolytes, solid electrolytes,gel electrolytes, and molten-salt gel electrolytes.

The liquid electrolytes may be liquid materials containing redoxspecies. Any liquid electrolyte that is commonly used in the field ofsolar cells may be used without any particular limitation. Examples ofthe liquid electrolyte that may be used include a liquid electrolytecontaining a redox species and a solvent capable of dissolving the redoxspecies, a liquid electrolyte containing a redox species and a moltensalt capable of dissolving the redox species, and a liquid electrolytecontaining a redox species, a solvent, and a molten salt, the solventand the molten salt being capable of dissolving the redox species.

Examples of the redox species include an I⁻/I³⁻ system, a Br²⁻/Br³⁻system, an Fe²⁺/Fe³⁺ system, and a quinone/hydroquinone system. Specificpreferred examples thereof include combinations of iodine (I₂) with ametal iodide, e.g., lithium iodide (LiI), sodium iodide (NaI), potassiumiodide (KI), or calcium iodide (CaI₂); combinations of iodine with atetraalkylammonium salt, e.g., tetraethylammonium iodide (TEAT),tetrapropylammonium iodide (TPAI), tetrabutylammonium iodide (TBAI), ortetrahexylammonium iodide (THAI); and combinations of bromine with ametal bromide, e.g., lithium bromide (LiBr), sodium bromide (NaBr),potassium bromide (KBr), or calcium bromide (CaBr₂). Among thesecompounds, the combination of I₂ with LiI is particularly preferred.

Examples of a solvent for the redox species include carbonate compounds,such as propylene carbonate; nitrile compounds, such as acetonitrile;alcohols, such as ethanol; water; and aprotic polar substances. Amongthese compounds, carbonate compounds and nitrile compounds areparticularly preferred. These solvents may also be used in combinationof two or more as a mixture.

The solid electrolytes may be conductive materials which are capable oftransporting electrons, holes, and ions, which can be used aselectrolytes for solar cells, and which have no flowability. Specificexamples thereof include hole-transport materials, such aspolycarbazole; electron-transport materials, such astetranitrofluorenone; conductive polymers, such as polylol;polyelectrolytes prepared by solidifying liquid electrolytes withmacromolecular compounds; p-type semiconductors, such as copper iodideand copper thiocyanate; and electrolytes prepared by solidifying liquidelectrolytes containing molten salts with fine particles.

The gel electrolytes are each composed of an electrolyte and a gellingagent, in general. Examples of the gelling agent include organic gellingagents, such as cross-linked polyacrylic resin derivatives, cross-linkedpolyacrylonitrile derivatives, polyalkylene oxide derivatives, siliconeresins, and polymers each having a nitrogen-containing heterocyclicquaternary compound salt structure in a side chain.

Usually, the molten-salt gel electrolytes are each composed of theforegoing gel electrolyte and an ambient temperature molten salt.Examples of the ambient-temperature molten salt includenitrogen-containing heterocyclic quaternary ammonium salt compounds,such as pyridinium salts and imidazolium salts.

The foregoing electrolyte may contain an additive as needed. Examples ofthe additive include nitrogen-containing aromatic compounds, such astert-butylpyridine (TBP); and imidazole salts, such asdimethylpropylimidazole iodide (DMPII), methylpropylimidazole iodide(MPII), ethylmethylimidazole iodide (EMIT), ethylimidazole iodide (EII),and hexylmethylimidazole iodide (HMII).

An electrolyte concentration in the electrolyte preferably is preferablyin the range of 0.001 mol/L or more and 1.5 mol/L or less and morepreferably 0.01 mol/L or more and 0.7 mol/L or less. In the case wherethe supporting substrate 8 serves as a light-receiving surface in adye-sensitized solar cell module, incident light reaches thephotoelectric conversion layer 3 through an electrolytic solution toexcite carriers. This may cause a reduction in the performance of thesolar cell, depending on the electrolyte concentration. Thus, theelectrolyte concentration is preferably set in view of this factor.

<<Porous Insulating Layer>>

In the present invention, the porous insulating layer 4 is arranged incontact with the photoelectric conversion layer 3. The porous insulatinglayer 4 reduces a leakage current from the photoelectric conversionlayer 3 to the counter conductive layer 7. The porous insulating layeris preferably arranged in contact with an upper portion and sidesurfaces of the photoelectric conversion layer 3. This is because byarranging the porous insulating layer so as to cover the upper portionand the side surfaces of the photoelectric conversion layer 3 asdescribed above, the leakage current from the photoelectric conversionlayer 3 is reduced.

Examples of a material contained in the porous insulating layer 4include niobium oxide, zirconium oxide, silicon oxide, such as silicaglass and soda glass, aluminum oxide, and barium titanate. Thesematerials may be used separately or in combination of two or more. Thematerial used for the porous insulating layer 4 is preferably in theform of particles. The average particle size thereof is preferably 5 to500 nm and more preferably 10 to 300 nm. Titanium oxide or rutiletitanium oxide having a particle size of 100 nm to 500 nm may bepreferably used.

The porous insulating layer 4 is preferably composed of a materialhaving an electrical conductivity of 1×10¹² Ω·cm or less. A lowerelectrical conductivity is more preferred. The use of the materialhaving an electrical conductivity as described above results in areduction in the leakage current from the photoelectric conversion layer3 to the counter conductive layer 7. If the porous insulating layer 4 iscomposed of a material having an electrical conductivity of more than1×10¹² Ω·cm, the leakage current flows easily to reduce the fill factorand so forth. This leads to a reduction in photoelectric conversionefficiency, which is not preferred.

The porous insulating layer 4 preferably has a thickness of 0.2 μm ormore and 5 μm or less and more preferably 0.5 μm or more and 2 μm orless. A thickness of the porous insulating layer 4 of more than 5 μm isnot preferred because the light-scattering effect of the reflectivelayer is inhibited to reduce a short-circuit current (Jsc). A thicknessof the porous insulating layer 4 of less than 0.2 μm is not preferredbecause the leakage current is easily generated.

<<Reflective Layer>>

In the present invention, the reflective layer 5 is arranged on theporous insulating layer 4. The reflective layer 5 can reflect lightpassing through the photoelectric conversion layer 3 and allow thereflected light to enter the photoelectric conversion layer 3 again. Inthis way, the entrance of light reflected from the photoelectricconversion layer 3 enables the photoelectric conversion efficiency toincrease. The reflective layer 5 is preferably arranged so as to be incontact with an upper portion of the porous insulating layer 4 and so asto have a larger area than that required to cover the photoelectricconversion layer. More preferably, the reflective layer 5 is arranged onthe upper surface of the porous insulating layer 4 so as to have thesame shape as the porous insulating layer 4. As described above, thereflective layer 5 is arranged so as to cover the entire surface of theporous insulating layer; hence, the reflective layer 5 can reflect lightpassing through the photoelectric conversion layer 3 to allow the lightto enter the photoelectric conversion layer again.

The reflective layer 5 may be composed of any material capable ofreflecting equivalent light. Examples of the material that may be usedinclude titanium oxide, aluminum oxide, and barium titanate. Among thesematerials, the reflective layer 5 more preferably contains aluminumoxide or titanium oxide. Still more preferably, the reflective layer 5is composed of a material identical to that constituting the poroussemiconductor.

In the reflective layer 5, a higher proportion of fine particles havingan average particle size larger than the fine particles constituting theporous semiconductor is preferred. More preferably, the reflective layer5 is formed of only fine particles having an average particle sizelarger than the fine particles constituting the porous semiconductor.The reflective layer 5 preferably has a thickness of 5 μm or more. Athickness of the reflective layer 5 of less than 5 μm results in areduction in the reflectance of light and, in addition, is more likelyto bring the catalyst layer and the counter conductive layer arranged onthe reflective layer into contact with the porous semiconductor or atransparent electrode layer, which is not preferred.

Here, the total thickness of the porous insulating layer and thereflective layer is preferably 10 μm or more and more preferably 11 μmor more and 20 μm or less. A total thickness of the porous insulatinglayer and the reflective layer of less than 10 μm is not preferredbecause the catalyst layer and the counter conductive layer arranged onthe reflective layer are more likely to come into contact with theporous semiconductor or a transparent electrode layer. A total thicknessof the porous insulating layer and the reflective layer of more than 20μm is not preferred because the transport resistance of thecarrier-transport material is increased. In the case where thereflective layer is arranged on the porous insulating layer and wherethe total thickness thereof is within the above range, the effect of aninsulating layer to inhibit leakage is imparted to the reflective layer.

<<Catalyst Layer>>

In the present invention, the catalyst layer 6 is arranged in contactwith the counter conductive layer 7. The presence of the catalyst layer6 provides the efficient transfer of electrons from the counterconductive layer 7. Any material may be used for the catalyst layer 6without any particular limitation as long as the material can transferelectrons on a surface thereof. Examples thereof include noble metals,such as platinum and palladium; and carbonaceous materials, such ascarbon black, Ketjenblack, carbon nanotubes, and fullerenes.

<<Counter Conductive Layer>>

In the present invention, the counter conductive layer 7 is notparticularly limited as long as it is conductive. The counter conductivelayer 7 may not necessarily be optically transparent. However, in thecase where the supporting substrate 8 serves as a light-receivingsurface, the counter conductive layer 7 needs to be opticallytransparent, as with the transparent conductive layer.

As a material contained in the counter conductive layer 7, for example,complex indium tin oxide (ITO), tin oxide (SnO₂), fluorine-doped tinoxide (FTO), or zinc oxide (ZnO) (ITO) may be used. Alternatively, ametal that is not corroded by the electrolytic solution, for example,titanium, nickel, or tantalum, may be used. And also, as a materialcontained in the counter conductive layer 7, a material havingconductivity and catalytic ability such as carbon or platinum may beused. When material having conductivity and catalytic ability is usedfor the counter conductive layer 7, the catalyst layer 6 may be omitted.The counter conductive layer 7 composed of such a material may be formedby a known method, for example, a sputtering method or a spray method.

The counter conductive layer 7 preferably has a thickness of about 0.02μm to about 5 μm. A lower resistance of the counter conductive layer 7is better. The counter conductive layer 7 preferably has a resistance of40 Ω/sq or less. In the case where a material constituting the counterconductive layer 7 has a dense structure, a plurality of pores arepreferably formed in the counter conductive layer 7 in order tofacilitate the adsorption of the photosensitizer and facilitate thepassage of the carrier-transport material.

The counter conductive layer 7 may be subjected to physical contact orlaser processing to form the pores. The size of each of the pores ispreferably in the range of about 0.1 to about 100 μm and more preferablyabout 1 to about 50 μm. The distance between the pores is preferably inthe range of about 1 to about 200 μm and more preferably about 10 toabout 300 μm. The same effect is provided by forming stripe-shapedopening portions in the counter conductive layer 7. The distance betweenthe stripe-shaped opening portions is preferably in the range of about 1μm to about 200 μm and more preferably about 10 μm to about 300 μm.

<<Supporting Substrate>>

In the present invention, it is necessary to use the supportingsubstrate 8 capable of holding the carrier-transport material 11 thereinand preventing infiltration of water or the like from the outside. Inthe case where the supporting substrate 8 serves as a light-receivingsurface, the supporting substrate 8 is required to have opticaltransparency comparable to that of the transparent substrate. It is thusnecessary to use the same material as that of the transparent substrate1. For example, tempered glass is preferably used for the supportingsubstrate 8 in view of the case where the photoelectric conversionelement is placed outdoors.

Preferably, the supporting substrate 8 (including the catalyst layer andthe counter conductive layer when they are arranged on a surface) is notin contact with the photoelectric conversion layer 3 on the transparentsubstrate 1. It is thus possible to hold a sufficient amount of thecarrier-transport material in the photoelectric conversion element. Thesupporting substrate 8 is preferably equipped with an inlet to injectthe carrier-transport material. It is possible to inject thecarrier-transport material through the inlet by a vacuum injectionmethod, a vacuum impregnation method, or the like. The supportingsubstrate 8 is not in contact with the photoelectric conversion layer 3on the transparent substrate 1. This results in an increase in injectionrate when the carrier-transport material is injected through the inlet.It is thus possible to improve the production tact of the photoelectricconversion element and the photoelectric conversion element module.

<<Sealing Member>>

In the present invention, the sealing member 9 is arranged to bond thetransparent substrate 1 to the supporting substrate 8. The sealingmember 9 is preferably composed of a silicone resin, an epoxy resin, apolyisobutylene resin, a hot-melt resin, a glass-based material, or thelike. The sealing member 9 may have a laminated structure containing twoor more thereof.

Examples of a material contained in the sealing member 9 include Model31X-101, manufactured by ThreeBond Co., Ltd., Model 31X-088,manufactured by ThreeBond Co., Ltd., and commonly-marketed epoxy resins.In the case where the sealing member 9 is formed of a silicone resin, anepoxy resin, or a glass frit, the sealing member 9 is preferably formedwith a dispenser. In the case where the sealing member 9 is formed of ahot-melt resin, the sealing member 9 may be formed by forming a holepattern in a sheet-like hot-melt resin.

<<Method for Forming Porous Semiconductor>>

A method for forming the porous semiconductor constituting thephotoelectric conversion layer 3 on the transparent conductive layer 2is not particularly limited. A known method may be employed. That is,for example, the porous semiconductor is formed by applying a suspensioncontaining semiconductor fine particles suspended in an appropriatesolvent to a predetermined site using a known method and performing atleast one of drying and firing.

In the case where the photoelectric conversion layer 3 is formed so asto be in contact with the sealing member 9, it is preferred that thesuspension be prepared so as to have a low viscosity and that thesuspension be applied to a region divided by the sealing member 9 with adispenser or the like. In this case, the paste spreads to an end portionof the region and levels easily under its own weight.

Examples of the solvent used for the suspension include glyme-basedsolvents, such as ethylene glycol monomethyl ether; alcohols, such asisopropyl alcohol; alcohol-based mixed solvents, such as isopropylalcohol/toluene; and water. A commercially titanium oxide paste (forexample, Ti-nanoxide T, D, T/SP, or D/SP, manufactured by Solaronix) maybe used in place of the suspension.

After the resulting suspension is applied onto the transparentconductive layer 2, at least one of drying and firing is performed toform the porous semiconductor on the transparent conductive layer 2. Asa method for applying the suspension, a known method, e.g., a doctorblade method, a squeegee method, a spin coating method, or a screenprinting method, may be employed.

Conditions (for example, temperature, time, and an atmosphere) requiredfor the drying or firing of the porous semiconductor may beappropriately set, depending on the type of semiconductor fineparticles. For example, in the case where drying or firing is performedin an air atmosphere or in an inert gas atmosphere, drying or firing ispreferably performed at about 50° C. to about 800° C. for about 10seconds to about 12 hours. The drying or firing may be performed once ata temperature or twice or more at different temperatures.

The porous semiconductor may be formed of a laminate in which aplurality of layers are stacked. To form the laminate of the poroussemiconductor, it is preferred that suspensions containing differentsemiconductor fine particles be prepared and that at least one ofapplication, drying, and firing be repeated twice or more.

After the formation of the porous semiconductor in this way,post-treatment is preferably performed in order to improve theperformance of the porous semiconductor. The post-treatment of theporous semiconductor results in improvement in the electrical connectionbetween semiconductor fine particles, an increase in the surface area ofthe porous semiconductor, and a reduction in defect level on thesemiconductor fine particles. For example, the porous semiconductorcomposed of titanium oxide is post-treated with an aqueous solution oftitanium tetrachloride, thereby improving the performance of the poroussemiconductor.

<<Formation of Porous Insulating Layer>>

Next, the porous insulating layer 4 is formed on the photoelectricconversion layer 3. The porous insulating layer 4 may be formed in thesame way as the porous semiconductor. That is, an insulating substancein the form of the fine particles described above is dispersed in anappropriate solvent. A macromolecular compound, e.g., ethyl cellulose orpolyethylene glycol (PEG), is mixed therewith to prepare a paste. Theresulting paste is applied onto the photoelectric conversion layer 3. Atleast one of drying and firing is performed, thereby forming the porousinsulating layer 4 on the photoelectric conversion layer 3.

<<Adsorption of Photosensitizer>>

Next, the photosensitizer is allowed to adsorb on the poroussemiconductor to form the photoelectric conversion layer 3. A method foradsorbing the photosensitizer is not particularly limited. For example,a method in which the porous semiconductor is immersed in the foregoingdye adsorption solution may be employed. In this case, the dyeadsorption solution may be heated in order to infiltrate the dyeadsorption solution into the deep portions of micropores of the poroussemiconductor.

As a solvent to dissolve the photosensitizer, any solvent may be used aslong as it can dissolve the photosensitizer. Examples thereof includealcohols, toluene, acetonitrile, tetrahydrofuran (THF), chloroform, anddimethylformamide. A purified solvent is preferably used as the solvent.A mixture of two or more types of solvents may be used.

The concentration of the dye contained in the dye adsorption solutionmay be appropriately set, depending on the types of dye and solvent,conditions of a dye adsorption step, and so forth. To improve anadsorption function, a high concentration is preferred. For example, theconcentration is preferably 1×10⁻⁵ mol/L or more. When the dyeadsorption solution is prepared, heating may be performed in order toimprove the solubility of the dye.

<<Formation of Reflective Layer>>

The reflective layer 5 is formed on the resulting porous insulatinglayer 4 described above. As a method for forming the reflective layer 5,the same method as the method for forming the photoelectric conversionlayer may be employed.

<<Photoelectric Conversion Element Module>>

The present invention also provides a photoelectric conversion elementmodule including two or more photoelectric conversion elementselectrically connected in series, in which at least one of the two ormore photoelectric conversion elements is the photoelectric conversionelement of the present invention. FIG. 2 is a schematic cross-sectionalview of an example of the structure of a photoelectric conversionelement module of the present invention. A photoelectric conversionelement module 20 in FIG. 2 is one in which four photoelectricconversion elements of the present invention are connected. Asillustrated in FIG. 1, each of the photoelectric conversion elementsincludes a transparent substrate 21, a transparent conductive layer 22on the transparent substrate 21, a photoelectric conversion layer 23 onthe transparent conductive layer 22, a porous insulating layer 24 incontact with the photoelectric conversion layer 23, a reflective layer25 in contact with the porous insulating layer 24, and a catalyst layer26 on the reflective layer 25, in which the area of the orthogonalprojection of the porous insulating layer 24 onto the transparentsubstrate 21 and the area of the orthogonal projection of the reflectivelayer 25 onto the transparent substrate 21 are each larger than the areaof the orthogonal projection of the photoelectric conversion layer 23onto the transparent substrate 21.

Gaps among the photoelectric conversion layer 23, the porous insulatinglayer 24, the reflective layer 25, and the catalyst layer 26 are filledwith the carrier-transport material. A counter conductive layer 27 isarranged on the catalyst layer 26. The transparent substrate 21 isconnected to a supporting substrate 28 with a sealing member 29. Thetransparent conductive layer 22 is partially broken. The broken portionsare referred to as scribe lines 22′. Collector electrodes 32 arearranged at end portions of the transparent substrate 21.

The photoelectric conversion element module of the present invention isnot limited to the module illustrated in FIG. 2. A module in which twoor more photoelectric conversion elements are electrically connected inseries and/or parallel is also included and does not depart from thepresent invention as long as at least one of two or more photoelectricconversion elements is a photoelectric conversion element of the presentinvention. The photoelectric conversion element module preferablyincludes three or more photoelectric conversion elements.

EXAMPLES

While the present invention will be described in more detail below byexamples, the present invention is not limited to these examples.Hereinafter, thickness values of layers are determined by measurementwith a surface roughness and texture measuring instrument (trade name:SURFCOM 1400A, manufactured by TOKYO SEIMITSU CO., LTD.) unlessotherwise specified.

Example 1

In this example, the photoelectric conversion element 10 illustrated inFIG. 1 was produced. A 15 mm×40 mm×1.5 mm thick transparent electrodesubstrate (glass with a SnO₂ film, manufactured by Nippon Sheet GlassCompany, Ltd) was prepared. The transparent electrode substrate includesthe transparent conductive layer 2 composed of fluorine-doped SnO₂ onthe transparent substrate 1 composed of glass.

The transparent conductive layer 2 on the transparent electrodesubstrate was cut by laser scribing to form the scribe line 2′. Acommercially available titanium oxide paste (trade name: D/SP,manufactured by Solaronix) was applied onto the transparent conductivelayer 2 with a screen printing machine (Model: LS-150, manufactured byNewlong Seimitsu Kogyo Co., Ltd.) using a screen plate having a 5 mm×30mm pattern. Leveling was performed at room temperature for 1 hour.

The resulting coating film of the titanium oxide paste was dried in anoven set at 80° C. for 20 minutes. The resulting coating film was thenfired with a firing furnace (Model: KDF P-100, manufactured by DenkenCo., Ltd.) set at 500° C. in air for 60 minutes. The application andfiring of the titanium oxide paste were repeated four times in the sameway as described above, thereby producing a porous semiconductor havinga thickness of 25 μm.

A paste containing zirconia particles with an average particle size of50 nm was applied onto the porous semiconductor with a screen printingmachine using a screen plate having a 7 mm×38 mm pattern. The paste wasfired at 500° C. for 60 minutes to form the porous insulating layer 4having a flat portion with a thickness of 4 μm. The electricalconductivity of the porous insulating layer 4 was measured with animpedance analyzer (product name: 1255 (manufactured by Solartron)) andfound to be 2×10¹³ Ω·cm.

A paste containing titanium oxide particles having an average particlesize of 300 nm was applied with a screen plate having the same patternas the screen plate used for the production of the porous insulatinglayer 4. The paste was fired at 500° C. for 60 minutes to form thereflective layer 5 having a flat portion with a thickness of 11 μm.Thus, the total thickness of the porous insulating layer 4 and thereflective layer 5 was 15 μm.

The catalyst layer 6 composed of Pt was formed by evaporation on aportion of the reflective layer 5 located directly above the poroussemiconductor. The catalyst layer 6 had the same size as the poroussemiconductor. The counter conductive layer 7 having a size of 9 mm×36mm was formed by evaporation on the catalyst layer 6.

A dye (trade name: Ruthenium 620 1H3TBA, manufactured by Solaronix)represented by formula (2) was dissolved in a mixed solvent ofacetonitrile and tert-butanol in a volume ratio of 1:1 to prepare a dyeadsorption solution having a dye concentration of 4×10⁻⁴ mol/L.

The foregoing porous semiconductor was immersed in the dye adsorptionsolution. The state was maintained at room temperature for 100 hours.Then the porous semiconductor was washed with ethanol and dried at about60° C. for about 5 minutes to allow the dye to adsorb on the poroussemiconductor. In this way, the photoelectric conversion layer 3composed of the porous semiconductor on which the dye adsorbs.

As the supporting substrate 8, a 11 mm×40 mm glass substrate was used.The supporting substrate 8 and the transparent substrate 1 were bondedtogether using a heat-sealing film with an opening portion (Himilan1702, manufactured by E.I. du Pont de Nemours and Company). Heating wasperformed in an oven set at about 100° C. for 10 minutes to press-bondthe supporting substrate 8 and the transparent substrate 1. Thisheat-sealing film serves as the sealing member 9.

A carrier-transport material that has been previously prepared wasinjected through an inlet to inject an electrolytic solution, the inletbeing arranged in the supporting substrate 8. A mixture containingacetonitrile serving as a solvent, LiI (manufactured by Aldrich) servingas a redox species in a concentration of 0.1 mol/L, I₂ (manufactured byKISHIDA CHEMICAL Co., Ltd.) serving as a redox species in aconcentration of 0.01 mol/L, tert-butylpyridine (manufactured byAldrich) serving as an additive in a concentration of 0.5 mol/L, anddimethylpropylimidazole iodide (manufactured by SHIKOKU CHEMICALSCORPORATION) serving as an additive in a concentration of 0.6 mol/L wasprepared and used as the carrier-transport material.

The inlet to inject the electrolytic solution was sealed with anultraviolet curable resin (Model: 31X-101 229, manufactured by ThreeBondCo., Ltd.), thereby completing a photoelectric conversion element(single cell) according to this example. A Ag paste (trade name: Dotite,manufactured by Fujikura Kasei Co., Ltd.) was applied to the transparentsubstrate 1 of the resulting photoelectric conversion element to formcollector electrodes.

Examples 2 to 4

Photoelectric conversion elements of Examples 2 to 4 were produced as inExample 1, except that the thicknesses of the porous insulating layerswere different from those in Example 1 as described in Table 1.

Example 5

A photoelectric conversion element of Example 5 was produced as inExample 1, except that the material of the porous insulating layer waschanged to silicon oxide.

Example 6

A photoelectric conversion element of Example 6 was produced as inExample 1, except that the material of the reflective layer was changedto aluminum oxide.

Comparative Example 1

A photoelectric conversion element of Comparative Example 1 was producedas in Example 1, except that the reflective layer having the same sizeas the porous semiconductor was formed.

Example 7

In this example, a photoelectric conversion element module having thestructure illustrated in FIG. 2 was produced. A 50-mm-long and37-mm-wide transparent electrode substrate (glass with a SnO₂ film,manufactured by Nippon Sheet Glass Company, Ltd) was prepared. Thetransparent electrode substrate includes the transparent conductivelayer 22 composed of SnO₂ on the transparent substrate 21 composed ofglass.

The transparent conductive layer 22 was cut by laser scribing to formthe scribe lines 22′ arranged in parallel with one another in thelongitudinal direction, each of the scribe lines 22′ having a width of60 μm. The scribe lines 22′ were formed at four positions in total, thefour positions being spaced at 7 mm intervals from a position 9.5 mmaway from the left end portion of the transparent substrate 21.

A 30-mm-long, 5-mm-wide, and 25-μm-thick porous semiconductor was formedin the same way as in Example 1, the porous semiconductor being centeredat a position away from 6.9 mm from the left end portion of thetransparent substrate 21. Three porous semiconductors each having thesame size were formed at 7 mm intervals from the position.

The porous insulating layers 24 were formed on the porous semiconductorsas in the same way as in Example 1. A 46-mm-long and 5.6-mm-wide porousinsulating layer 24 was formed so as to be centered at a position 6.9 mmaway from the left end of the transparent substrate 21. Three porousinsulating layers each having the same size were formed at 7 mmintervals from the center of this porous insulating layer 24.

The reflective layers 25 were formed on the porous insulating layers 24in the same way as in Example 1. The catalyst layers 26 composed of Ptwere formed on the reflective layers 25. Each of the catalyst layers 26had the same position and the same size as a corresponding one of theporous semiconductors. The counter conductive layers 27 were formed inthe same way as in Example 1. A 44-mm-long and 5.6-mm-wide counterconductive layer 27 was formed so as to be centered at a position 7.2 mmaway from the left end portion of the transparent substrate 21. Threecounter conductive layers 27 having the same size were formed at 7 mmintervals from the center of the leftmost porous insulating layer 24.

The four porous semiconductors were immersed in the dye adsorptionsolution used in the Example 1 and maintained at room temperature for120 hours, thereby allowing the dye to adsorb on the poroussemiconductors. An ultraviolet curable resin (31X-101, manufactured byThreeBond Co., Ltd.) was applied between the photoelectric conversionlayers 23 and around the transparent substrate 21 with a dispenser(ULTRASAVER, manufactured by EFD). The supporting substrate 28 formed ofa 60-mm-long and 30-mm-wide glass substrate was bonded thereto andirradiated with ultraviolet rays using an ultraviolet lamp (NOVACURE,manufactured by EFD), thereby curing the ultraviolet curable resin toform the sealing member 29.

A carrier-transport material was injected in the same way as inExample 1. The inlet was sealed with the ultraviolet curable resin,thereby completing the photoelectric conversion element module of thisExample. A Ag paste (trade name: Dotite, manufactured by Fujikura KaseiCo., Ltd.) was applied onto the transparent substrate of thephotoelectric conversion element module to form collector electrodeportions.

Example 8

The laminate of the photoelectric conversion element produced in Example1 was cut in the series direction by laser scribing to divide thephotoelectric conversion element into two photoelectric conversionelements. The resulting two photoelectric conversion elements wereconnected in parallel to produce a photoelectric conversion elementmodule of this example.

Comparative Example 2

A photoelectric conversion element module of Comparative Example 2 wasproduced in the same way as in Example 7, except that the shape of thereflective layers was the same as that of the porous semiconductors andthat the thicknesses of the porous insulating layers and the reflectivelayers were equal to those in Comparative Example 1.

<Solar Cell Characteristics of Photoelectric Conversion Elements ofExamples 1 to 6 and Comparative Example 1>

A black mask having an opening portion with an area of 1.5 cm² wasarranged on a light-receiving surface of each of the photoelectricconversion elements of Examples 1 to 6 and Comparative Example 1. Ashort-circuit current Jsc (mA/cm²), an open voltage Voc (V), a fillfactor (FF), and a photoelectric conversion efficiency (%) were measuredby irradiating the light-receiving surface of each of the photoelectricconversion elements with light having an intensity of 1 kW/m² using AM1.5 solar simulator. Table 1 illustrates the results.

<Solar Cell Characteristics of Photoelectric Conversion Elements ofExamples 7 and 8 and Comparative Example 2>

A black mask having an opening portion with an area of 7.8 cm² wasarranged on a light-receiving surface of each of the photoelectricconversion elements of Examples 7 and 8. A short-circuit current Jsc(mA/cm²), an open voltage Voc (V), a fill factor (FF), and aphotoelectric conversion efficiency (%) were measured by irradiating thelight-receiving surface of each of the photoelectric conversion elementswith light having an intensity of 1 kW/m² using AM 1.5 solar simulator.Table 1 illustrates the results.

TABLE 1 Porous insulating Conversion layer Jsc Voc efficiency (μm)(mA/cm²) (V) FF (%) Example 1 4 20.21 0.701 0.681 9.648 Example 2 520.08 0.702 0.679 9.571 Example 3 7 19.90 0.703 0.676 9.457 Example 4 220.52 0.700 0.682 9.796 Example 5 4 20.55 0.702 0.685 9.882 Example 6 420.31 0.701 0.680 9.681 Comparative 4 19.20 0.602 0.305 3.525 Example 1Example 7 4 4.31 2.831 0.665 8.11 Example 8 4 4.21 2.835 0.660 7.88Comparative 4 3.86 2.840 0.658 7.21 Example 2

In Table 1, a comparison of the photoelectric conversion elements ofExamples 1 to 6 with the photoelectric conversion element of ComparativeExample 1 demonstrates the following: In Examples 1 to 6, the area ofthe orthogonal projection of the photoelectric conversion layer 3 ontothe transparent substrate 1 is larger than the area of the orthogonalprojection of each of the porous insulating layer 4 and the reflectivelayer 5, thereby improving the short-circuit current density and thephotoelectric conversion efficiency. In the photoelectric conversionelement of Comparative Example 1, the photoelectric conversion layer 3and the reflective layer 5 are the same in size, thereby reducing thelight-scattering effect. Furthermore, in Example 1, a short circuitoccurred to reduce the fill factor and the photoelectric conversionefficiency presumably because of the insufficient thickness of each ofthe porous insulating layer and the reflective layer, which wereportions other than the photoelectric conversion layer.

A comparison of the dye-sensitized solar cell modules of Examples 7 to 8with that of Comparative Example 2 also leads to the same conclusion asthe comparison of Examples 1 to 6 and Comparative Example 1.

While the embodiments and examples of the present invention have beendescribed as above, proper combinations of the structures of theembodiments and examples are planned from the outset.

It should be understood that the embodiments and the examples disclosedherein are illustrative and not limitative in any respect. The scope ofthe present invention is defined by the terms of the claims, rather thanthe description of the embodiments above, and is intended to include anymodifications within the scope and meaning equivalent to the terms ofthe claims.

REFERENCE SIGNS LIST

1, 21, 41 transparent substrate, 2′, 22′ scribe line, 2, 22, 42transparent conductive layer, 3, 23 photoelectric conversion layer, 4,24, 44 porous insulating layer, 5, 25, 45 reflective layer, 6, 26, 46catalyst layer, 7, 27, 47 counter conductive layer, 8, 28, 48 supportingsubstrate, 9, 29, 49 sealing member, 10, 40 photoelectric conversionelement, 11, 51 carrier-transport material, 20 photoelectric conversionelement module, 32 collector electrode, 43 porous semiconductor.

1. A photoelectric conversion element comprising: a transparentsubstrate; a first transparent conductive layer arranged on thetransparent substrate; a second transparent conductive layer arranged onthe transparent substrate; a photoelectric conversion layer arranged onthe first transparent conductive layer; a porous insulating layercovering a top surface of the photoelectric conversion layer, a sidesurface of the photoelectric conversion layer and a surface of thetransparent substrate between the first transparent conductive layer andthe second transparent conductive layer; a reflective layer arranged onthe porous insulating layer and covering a a top surface and a sidesurface of the porous insulating layer; and a counter conductive layerarranged on the reflective layer and extending along the reflectivelayer to the second transparent conductive layer; wherein thephotoelectric conversion layer comprises: a porous semiconductor, acarrier-transport material included in the porous semiconductor and aphotosensitizer included in the porous semiconductor, wherein thephotoelectric conversion layer, the porous insulating layer and thereflective layer are laminated in that order, and wherein the porousinsulating layer has an orthogonal projection onto the transparentsubstrate, the orthogonal projection of the porous insulating layer ontothe transparent substrate having an area, the reflective layer has anorthogonal projection onto the transparent substrate, the orthogonalprojection of the reflective layer onto the transparent substrate havingan area, the photoelectric conversion layer has an orthogonal projectiononto the transparent substrate, the orthogonal projection of thephotoelectric conversion layer onto the transparent substrate having anarea, and the area of the orthogonal projection of the porous insulatinglayer onto the transparent substrate and the area of the orthogonalprojection of the reflective layer onto the transparent substrate areeach larger than the area of the orthogonal projection of thephotoelectric conversion layer onto the transparent substrate.
 2. Thephotoelectric conversion element according to claim 1, wherein thecounter conductive layer comprising a carbon or platinum.
 3. Thephotoelectric conversion element according to claim 1, wherein thereflective layer is thicker than the porous insulating layer.
 4. Thephotoelectric conversion element according to claim 1, wherein theporous insulating layer comprises one or more compounds selected fromthe group consisting of niobium oxide, zirconium oxide, silicon oxidecompounds, aluminum oxide, and barium titanate.
 5. The photoelectricconversion element according to claim 1, further comprising a catalystlayer arranged on the counter electrode.
 6. The photoelectric conversionelement according to claim 1, wherein the reflective layer comprisesaluminum oxide or titanium oxide.
 7. The photoelectric conversionelement according to claim 1, wherein the porous insulating layer isarranged in contact with an upper portion and side surfaces of thephotoelectric conversion layer, and the reflective layer is arranged incontact with an upper portion of the porous insulating layer.
 8. Thephotoelectric conversion element according to claim 1, wherein theporous insulating layer has a thickness of 0.2 μm or more and 5 μm orless.
 9. The photoelectric conversion element according to claim 1,wherein the total thickness of the porous insulating layer and thereflective layer is 10 μm or more.
 10. The photoelectric conversionelement according to claim 1, wherein the porous insulating layercomprises a material having an electrical conductivity of 1×10¹² Ω·cm orless.
 11. The photoelectric conversion element according to claim 1,wherein the reflective layer comprises a material identical to amaterial constituting the porous semiconductor.
 12. The photoelectricconversion element according to claim 1, wherein the reflective layerand the porous semiconductor are comprised of titanium oxide.
 13. Thephotoelectric conversion element according to claim 1, wherein thereflective layer is formed of fine particles having an average particlesize larger than the average particle size of fine particlesconstituting the porous semiconductor.
 14. A photoelectric conversionelement module comprising two or more photoelectric conversion elementselectrically connected in series, wherein at least one of thephotoelectric conversion elements is the photoelectric conversionelement according to claim
 1. 15. A photoelectric conversion elementmodule comprising three or more photoelectric conversion elementselectrically connected in series and/or parallel, wherein at least oneof the photoelectric conversion elements is the photoelectric conversionelement according to claim
 1. 16. A photoelectric conversion elementmodule comprising two or more photoelectric conversion elementselectrically connected in series and/or parallel, wherein each of thephotoelectric conversion elements is the photoelectric conversionelement according to claim 1.